Method and device for treating fluorine-containing water

ABSTRACT

A high percentage of fluorine in fluorine-containing water is removed and high purity calcium fluoride is recovered when treating the fluorine-containing water by passing the same through calcium carbonate packed towers provided in series in a plurality of stages, preferably two stages. In a method including passing fluorine-containing water through calcium carbonate packed towers provided in series in a plurality of stages to remove the fluorine in the fluorine-containing water and recover calcium fluoride, the calcium carbonate towers are packed with calcium carbonate with a volume mean diameter of 30 to 150 μm. By the use of calcium carbonate granules with a volume mean diameter of 30 to 150 μm, an increase in the purity of the recovered calcium fluoride and an increase in the fluorine removal ratio can be realized with a relatively small device.

FIELD OF INVENTION

The present invention relates to a method and a device for treatingfluorine-containing water, and more particularly relates to a method anda device for treating fluorine-containing water for removing fluorinehighly from fluorine-containing water such as waste water containing afluorine-based etching agent, and efficiently recovering the removedfluorine as calcium fluoride having high purity.

BACKGROUND OF INVENTION

A large amount of an etching agent which contains hydrogen fluoride orhydrogen fluoride and ammonium fluoride as main ingredients has beenused in a semiconductor manufacturing process, a related processthereof, or a surface treatment process of various materials includingmetal materials, single crystal materials, optical materials, and thelike. An etching agent which contains hydrogen fluoride as a mainingredient or an etching agent which contains hydrogen fluoride andammonium fluoride (buffered hydrofluoric acid) as main ingredientscontains high levels of fluorine as HF. Therefore, when these etchingagents flow into a waste water system, waste water thereof become tocontain fluorine at a high concentration. As materials treated withetching agents are washed with a large amount of cleaning water duringetching process and after the process, a large amount of waste watercontaining low levels of fluorine is discharged from the washingprocess.

According to a conventional method, waste water containing high levelsof fluorine and waste water containing low levels of fluorine are mixedand treated. Patent Document 1 discloses a method for treatingfluorine-containing waste water wherein the waste water is fed to andpassed through a reaction tower packed with granular calcium carbonate.

The method described in Patent Document 1, treatment is performed by amerry-go-round method, in which a plurality of towers packed withcalcium carbonate are arranged in series. First, raw water issequentially passed from a first tower (tower in a first stage) to thefollowing tower(s) to remove and recover fluorine. When the fluorineconcentration of the raw water flowing into the first tower and thefluorine concentration of the treated water flowed out from the firsttower become almost the same, feeding raw water to the first tower isstopped, the calcium fluoride is recovered from the first tower, and thefirst tower is packed with fresh calcium carbonate. Then, raw water isfed to and passed through the second tower, and flows sequentially tothe following tower(s) for the first tower.

Patent Document 1 describes that glanular calcium carbonate packed ineach calcium carbonate packed tower has a diameter of about 0.1 to 0.5mm, and specifically granular calcium carbonate having a diameter of0.25 mm is used in Examples thereof.

Patent Document 2 discloses a method for removing fluorine fromfluorine-containing raw water including a process of feeding the rawwater to a reaction tower packed with granular calcium carbonate toremove the fluorine, wherein acid or alkali is added to the raw waterbased on an α-value calculated from measured values of fluorineconcentration and acid concentration in the raw water.

LIST OF DOCUMENTS

Patent Document 1: Japanese Patent 3466637

Patent Document 2: Japanese Patent 2565110

The method described in Patent Document 1 has a problem that, in orderto recover high purity calcium fluoride from the calcium carbonatepacked towers, raw water is passed until the fluorine concentration ofthe raw water flowing into the tower in the first stage and the fluorineconcentration of the treated water therefrom become almost the same,i.e., the fluorine removal ratio of the calcium carbonate packed towerin the first stage becomes almost zero. As a result thereof, fluorineleaks into the treated water of the calcium carbonate packed tower(reaction tower) in the second stage as illustrated in FIG. 4, so thatthe fluorine removal ratio becomes low. For example, in Example 1 ofPatent Document 1, when the fluorine removal ratio of the first towerpacked with the calcium carbonate is 0%, the fluorine removal ratio ofthe second tower is 72.7 to 77.6%, i.e., the fluorine removal ratio ofthe entire device is 72.7 to 77.6%, so that treated water of high waterquality cannot be obtained.

In order to solve the above problem, it has also been designed toincrease the number of the towers packed with calcium carbonate and toarrange the calcium carbonate packed towers in series in three or morestages. However, in this case, the treating device is enlarged in itsscale, which is not preferable in every respect of the device cost,installation area, maintenance, and the like.

OBJECT AND SUMMARY OF INVENTION

It is an object of the present invention to solve the above-describedproblems, and provide a method and a device for treatingfluorine-containing water capable of removing fluorine influorine-containing water efficiently and recovering high purity calciumfluoride when treating the fluorine-containing water by passing the samethrough plurality of, preferably two, calcium carbonate packed towersarranged in series.

The present inventors have conducted extensive research for solving theabove-described problems, and have found that an increase in the purityof the recovered calcium fluoride and an increase in the fluorineremoval ratio can be realized with a relatively small device by the useof calcium carbonate granules having a specific volume mean granulediameter.

The present invention has been accomplished based on such findings, andthe gist thereof is described below.

A first aspect provides a method for treating fluorine-containing waterincluding passing fluorine-containing water through calcium carbonatepacked towers arranged in series in a plurality of stages to removefluorine in the fluorine-containing water and recover calcium fluoride,in which the calcium carbonate granules packed in each tower have avolume mean diameter of 30 to 150 μm.

A second aspect provides a method for treating fluorine-containing waterin which the calcium carbonate packed towers are arranged in series intwo stages in the first aspect.

A third aspect provides a method for treating fluorine-containing waterin which the calcium carbonate granules contain granules having adiameter of lower than 20 μm at a ratio of 15% or lower in the first orsecond aspect.

A fourth aspect provides a method for treating fluorine-containing waterin which the fluorine-containing water is passed through the calciumcarbonate packed towers at an SV of 0.1 to 5 hr⁻¹ in any one of thefirst to third aspects.

A fifth aspect provides a device for treating fluorine-containing water,having a unit for treating fluorine-containing water in which calciumcarbonate packed towers are provided in series in a plurality of stages,a unit for passing fluorine-containing water through the unit fortreating fluorine-containing water, a unit for extracting treated waterfrom the unit for treating fluorine-containing water, and a unit forrecovering calcium fluoride from the calcium carbonate packed towers, inwhich the volume mean diameter of the calcium carbonate packed in thecalcium carbonate packed towers is 30 to 150 μm.

A sixth aspect provides a device for treating fluorine-containing waterin which the calcium carbonate packed towers of the unit for treatingfluorine-containing water are arranged in series in two stages in thefifth aspect.

A seventh aspect provides a device for treating fluorine-containingwater in which the calcium carbonate granules contain granules having adiameter of lower than 20 μm at a ratio of 15% or lower in the fifth orsixth aspect.

An eighth aspect provides a device for treating fluorine-containingwater in which the fluorine-containing water is passed through thecalcium carbonate packed towers at an SV of 0.1 to 5 hr⁻¹ in any one ofthe fifth to seventh aspects.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an increase in the fluorine removalratio and an increase in the purity of calcium fluoride can be realizedwith a relatively small device by the use of calcium carbonate granuleshaving a specific volume mean diameter when passing fluorine-containingwater through a plurality of calcium carbonate packed towers in seriesto remove the fluorine in the fluorine-containing water and recover theremoved fluorine as calcium fluoride.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a system diagram illustrating an embodiment of a device fortreating fluorine-containing water of the invention.

FIG. 2 is a system diagram illustrating a first water passage directionin the device for treating fluorine-containing water of FIG. 1.

FIG. 3 is a system diagram illustrating a second water passage directionin the device for treating fluorine-containing water of FIG. 1.

FIG. 4 is a graph illustrating the breakthrough curve of fluorine in aconventional method (Diameter of calcium carbonate granules: 250 μm).

FIG. 5 is a graph illustrating the breakthrough curve of fluorine in amethod of the invention (Diameter of calcium carbonate granules: 90 μm).

DESCRIPTION OF EMBODIMENTS

Hereinafter, embodiments of a method and a device for treatingfluorine-containing water of the invention are described in detail withreference to the drawings.

FIG. 1 is a system diagram illustrating an embodiment of a device fortreating fluorine-containing water of the invention. FIGS. 2 and 3 aresystem diagrams illustrating water passage directions in the device fortreating fluorine-containing water. The devices of FIGS. 1 to 3 includecalcium carbonate packed towers 1 and 2, a raw water tank 3, a raw waterpump 4, a reaction liquid tank 5, a reaction liquid transfer pump 6, atreated water tank 7, and opening-and-closing valves V₁ to V₈. In FIGS.2 and 3, piping through which water passes is represented by a thickline and opened valves are represented by black and closed valves arerepresented by white.

The device for treating fluorine-containing water illustrated in FIG. 1is provided with water passage piping and valves in such a manner as torealize water passage of a merry-go-round system capable of switching afirst water passage direction in which raw water (fluorine-containingwater) is sequentially passed through the tower 1 and the tower 2 (FIG.2) and a second water passage direction in which raw water issequentially passed through the tower 2 and the tower 1 (FIG. 3).

The device for treating fluorine-containing water illustrated in FIG. 1is one example of the device for treating fluorine-containing water ofthe invention, and the invention is not limited to the device fortreating fluorine-containing water illustrated in FIG. 1. For example,the device can be configured so that the calcium carbonate packed towersare arranged in series in three or more stages. However, in terms of theobject of the invention of realizing an increase in the fluorine removalratio and an increase in the purity of the recovered calcium fluoridewithout increasing the size of the device, it is preferable to providethe calcium carbonate packed towers in series in two stages.

In FIG. 1, although water is passed through the towers 1 and 2 in anupward flow, the flow can be changed to a downward flow. However, in thetreatment of fluorine-containing water, carbonic acid gas is emitted asdescribed later due to a reaction of calcium carbonate and hydrogenfluoride. Therefore, in the case of a downward flow, a water breakphenomenon arises in the towers due to the gas flow, and the reaction ishindered by deflection of the water current. Therefore, an upward flowis preferable.

In the device for treating fluorine-containing water of FIG. 1, first,the valves V₁, V₃, V₅, and V₈ are opened and the valves V₂, V₄ V₆, andV₇ are closed as illustrated in FIG. 2. Then, raw water in the raw watertank 3 is passed through the tower 1 to supply outflow water of thetower 1 to the reaction liquid tank 5 with the raw water pump 4, theliquid in the reaction liquid tank 5 is passed through the calciumcarbonate packed tower 2 with the pump 6, and then the outflow water isextracted as treated water through the treated water tank 7.

Thus, the raw water is passed through the tower 1 and the tower 2 inthis order to be treated. When the fluorine removal ratio of the tower 1becomes almost 0% i.e., when the fluorine concentration of the inflowraw water of the tower 1 and the fluorine concentration of the outflowwater thereof becomes almost the same, the passage of the raw water intothe tower 1 is stopped. Then, packed granules containing calciumfluoride generated by the reaction of the calcium carbonate and thefluorine in the raw water in the tower 1 are recovered and also freshcalcium carbonate granules are packed in the tower 1. Thereafter, thewater passage direction of the raw water is switched to set thedirection to the water passage direction illustrated in FIG. 3.

Namely, the valves V₂, V₄, V₆, and V₇ are opened and the valves V₁, V₃,V₅, and V₈ are closed firstly. By this, the raw water in the raw watertank 3 is passed through the tower 2 to supply the outflow water of thetower 2 to the tank 5 with the pump 4. Then, the liquid in the tank 5 ispassed through the tower 1 with the pump 6, and then the outflow wateris extracted as treated water through the treated water tank 7.

Thus, the raw water is passed through the tower 2 and the tower 1 inthis order to be treated. When the fluorine removal ratio of the tower 2becomes almost 0% i.e., when the fluorine concentration of the inflowraw water of the tower 2 and the fluorine concentration of the outflowwater thereof becomes almost the same, the passage of the raw water intothe tower 2 is stopped. Then, packed granules containing calciumfluoride generated by the reaction of the calcium carbonate and thefluorine in the raw water in the tower 2 are recovered and also freshcalcium carbonate granules are packed in the tower 2. Thereafter, thewater passage direction of the raw water is switched to set thedirection to the water passage direction illustrated in FIG. 2.

Treatment thereafter is performed by switching the water passagedirection of FIG. 2 and the water passage direction of FIG. 3 asdescribed above.

In the invention, calcium carbonate granules having a volume meandiameter of 30 to 150 μm are used as the calcium carbonate to be packedin the calcium carbonate packed towers for treating fluorine-containingwater.

When the volume mean diameter of the calcium carbonate granules issmaller than 30 μm, fine calcium carbonate granules leak from thecalcium carbonate packed tower due to carbonic acid gas generated by thereaction of the calcium carbonate and the hydrogen fluoride in the rawwater, resulting that the treatment becomes unstable and that thefluorine removal ratio decreases.

In contrast, when the volume mean diameter of the calcium carbonategranules is larger than 150 μm, the reaction rate of the calciumcarbonate and the hydrogen fluoride is low, so that a sufficientfluorine removal ratio cannot be achieved by the two calcium carbonatepacked towers as described later. Moreover, the progress of the reactionto the inside of the calcium carbonate granules takes long time, so thatthe purity of the recovered calcium fluoride becomes low.

By the use of calcium carbonate granules having a volume mean diameterof 30 to 150 μm, preferably 30 to 100 μm, and more preferably 40 to 90μm, high purity calcium fluoride with a purity of 90% or more andpreferably 98% or more can be recovered and also a fluorine removalratio of 90% or more, preferably 97% or more, and more preferably 99% ormore can be achieved by the two calcium carbonate packed towers.

The calcium carbonate granules having the volume mean diameter of thecalcium carbonate granules in the above-described specific range havepreferably a ratio of fine calcium carbonate granules having a diameterof lower than 20 μm is 15% or lower, preferably 5% or lower, and morepreferably 1% or lower.

Even if the calcium carbonate granules have the volume mean diameter inthe above-described specific range, when the granules contain a largeamount of fine granules with a diameter of lower than 20 μm have atendency such that fine calcium carbonate granules leak from the calciumcarbonate packed towers due to the carbonic acid gas generated by thereaction of the calcium carbonate and the hydrogen fluorine in the rawwater, so that the treatment becomes unstable and the fluorine removalratio also decreases.

In the invention, the mechanism of the action of improving the effectsof the increase in the purity of the recovered calcium fluoride and theincrease in the fluorine removal ratio by the use of the calciumcarbonate granules with an appropriate volume mean diameter isconsidered as follows.

In the treatment of fluorine-containing water by calcium carbonate, thecalcium carbonate is changed to the calcium fluoride by the reaction ofhydrogen fluoride to the calcium carbonate represented by the followingreaction formula (1).

CaCO₃+2HF→CaF₂+H₂O+CO₂  (1)

This reaction gradually progresses from the surface of calcium carbonategranules. The reaction rate at this time can be represented by a modelequation represented by the following equation (2), and the reactionrate becomes high in inverse proportion to the square of the granuleradius.

$\begin{matrix}{{- r_{A}} = {\frac{3\varphi \; D_{Av}}{R^{2}}C_{Al}\frac{( {1 - x_{B}} )^{1/3}}{1 - ( {1 - x_{B}} )^{1/3}}}} & (2)\end{matrix}$

-   r_(A): Reaction rate, R: Particle radius

In terms of the reaction rate, the calcium carbonate granules arepreferable to have a small diameter. By reducing the diameter of thecalcium carbonate granules, the rising of the breakthrough curve offluorine becomes sharp as illustrated in FIG. 5, so that a high fluorineremoval ratio can be achieved even in the case where the calciumcarbonate packed towers (reaction towers) are arranged in two stages.When the diameter of the calcium carbonate granules is excessivelylarge, the substitution to calcium fluoride is not sufficientlyperformed to the inside of the calcium carbonate granules in some cases.Therefore, the diameter of the calcium carbonate granules is preferablyrelatively small also in terms of the purity of the recovered calciumfluoride. However, when the diameter of the calcium carbonate granulesis excessively small, fine granules of the calcium carbonate leak fromthe calcium carbonate packed towers due to carbonic acid gas generatedby the reaction of the calcium carbonate and the hydrogen fluoride, sothat the treatment becomes unstable, and the fluorine removal ratiodecreases.

In view of the above, calcium carbonate granules with a volume meandiameter of 30 to 150 μm, preferably 30 to 100 μm, and more preferably40 to 90 μm are used in the invention.

In the invention, when the flow rate of the raw water into the calciumcarbonate packed towers is too high, the reaction of the calciumcarbonate and the fluorine in the raw water does not sufficientlyprogress and a problem of leakage of fine granules arises. In contrast,when the flow rate is excessively low, the treatment efficiencydecreases. Therefore, the SV of the raw water flowing through thecalcium carbonate packed towers is preferably about 0.1 to 5 hr⁻¹ andmore preferably about 0.3 to 2 hr⁻¹.

The raw water flowing through the calcium carbonate packed towerspreferably has a pH of about 4 to 6. Therefore, it is preferable thatthe pH of the raw water is controlled as required, and thereafter theraw water is passed through the calcium carbonate packed towers.Moreover, as described in Patent Document 2, it is more preferable thatan a value is calculated from the fluorine concentration and the acidconcentration of the raw water, and then acid or alkali is added basedon the a value as an index to adjust the raw water.

Since the calcium fluoride recovered from the calcium carbonate packedtowers by the invention has high purity, the calcium fluoride can bereused as a raw material for manufacturing hydrofluoric acid. Thehydrofluoric acid is manufactured by reacting concentrated sulfuric acidwith calcium fluoride according to the reaction of the followingreaction formula (3). However, in this case, since the diameter of thecalcium carbonate granules for use in the invention is relatively small,the particle diameter of calcium fluoride obtained by the treatment ofthe raw water is also relatively small, so that the reaction rate withconcentrated sulfuric acid also becomes high. Therefore, the calciumfluoride thus obtained is suitable as a raw material for manufacturinghydrofluoric acid.

CaF₂+H₂SO₄→2HF+CaSO₄  (3)

The invention can be effectively applied to treatment of highconcentration fluorine-containing water with a fluorine concentration ofabout 2000 to 100000 mg/L which is discharged from a fluorine etchingprocess or the like, a low concentration fluorine-containing water witha fluorine concentration of about 20 to 1000 mg/L, or a mixed waterthereof.

EXAMPLES

Hereinafter, the invention is more specifically described with referenceto Examples and Comparative Examples.

The following Examples employed raw water prepared by diluting reagenthydrofluoric acid with pure water to adjust the concentration to 10,000mg-F/L (pH 3.5).

Example 1

150 ml of calcium carbonate granules with a volume mean diameter of 30μm were packed in each of two towers (columns) having an inner diameterof 20 mm. Calcium carbonate packed towers thus formed were arranged inseries in two stages as illustrated in FIG. 1. Then, raw water waspassed through the calcium carbonate packed tower 1 and the calciumcarbonate packed tower 2 in this order to be treated. The supply rate ofthe raw water pump 4 was 300 mL/hr and the SV of the water flowing intothe packed towers 1 and 2 was 2 hr⁻¹. When the fluorine concentrationsof the water flowing into the tower 1 and the water flowing outtherefrom became the same, feeding the raw water to the tower 1 wasstopped, the granules in the tower 1 were extracted, and then 150 ml offresh calcium carbonate granules with a volume mean diameter of 40 μmwere packed in the tower 1. After re-packing the calcium carbonate, theraw water was made flow through the tower 2 and the tower 1 in thisorder to be treated.

The results of measuring the fluorine ion concentration of the treatedwater and the total fluorine concentration and analyzing componentscontained in the extracted granules are shown in Table 1.

As shown in Table 1, in this Example, the treatment was stably performedwith a fluorine removal ratio of 90% or more. Moreover, the calciumfluoride purity of the recovered substance was 98% or more, so that ahigh purity calcium fluoride crystal was obtained.

Example 2

Example 2 was conducted in the same manner as in Example 1, except usingcalcium carbonate granules with a volume mean diameter of 90 μm. Theresults are shown in Table 1.

As shown in Table 1, in this Example 2, the treatment was stablyperformed with a fluorine removal ratio of 90% or more. Moreover, thecalcium fluoride purity of the recovered substance was 98% or more, sothat a high purity calcium fluoride crystal was obtained.

Example 3

Example 3 was conducted in the same manner as in Example 1, except usingcalcium carbonate granules with a volume mean diameter of 150 μm as thecalcium carbonate granules. The results are shown in Table 1.

As shown in Table 1, in this Example 3, the treatment was stablyperformed with a fluorine removal ratio of 90% or more. Moreover, thecalcium fluoride purity of the recovered substance was 98% or more, sothat a high purity calcium fluoride crystal was obtained.

Comparative Example 1

Comparative Example 1 was conducted in the same manner as in Example 1,except using calcium carbonate granules with a volume mean diameter of20 μm as the calcium carbonate granules. The results are shown in Table1.

In this Comparative Example 1, fine calcium carbonate granules leakedfrom the calcium carbonate packed towers due to carbonic acid gasgenerated by the reaction of the calcium carbonate and the hydrogenfluoride. Therefore, the fluorine removal ratio was lower than 90%, andthe treatment became unstable. When the fine granules which leaked wereanalyzed, it was found that fine granules with a diameter of lower than20 μm leaked.

Comparative Example 2

Comparative Example 2 was conducted in the same manner as in Example 1,except using calcium carbonate granules with a volume mean diameter of250 μm as the calcium carbonate granules. The results are shown in Table1.

In this Comparative Example 2, since the diameter of the calciumcarbonate granules was large, the reaction rate of the calcium carbonateand the hydrogen fluoride was low. Therefore, the treatment was notsufficiently performed by the two calcium carbonate packed towers, sothat the fluorine removal ratio was lower than 90%. Moreover, since theprogress of the reaction to the inside of the calcium carbonate granulestook long time, the calcium fluoride purity of the obtained recoveredsubstance was low as compared with that of the Examples.

TABLE 1 Volume mean CaF₂ diameter Raw water Treated water purity of ofcalcium T-F T-F F⁻ F removal recovered carbonate concentrationconcentration concentration ratio substance (μm) mg/L mg/L mg/L % %Example 1 30 10000 200~400  5~20 96~98 >98 Example 2 90 10000 10~3010~30 >99 >98 Example 3 150 10000 100~300 100~300 97~99 >98 Comparative20 10000 2300~4200 10~20 58~77 >98 Example 1 Comparative 250 100001000~1500 1000~1500 85~90 95~98 Example 2

Examples 4 to 7

Examples 4-7 were conducted in the same manner as in Example 2, exceptusing calcium carbonate granules with a volume mean diameter of 90 μmand having various granule size distributions as the calcium carbonategranules. The results are shown in Table 2.

Table 2 shows the following facts.

When fine granules are hardly contained (Example 4), the treatment wasstably performed with a fluorine removal ratio of 90% or more. Moreover,the calcium fluoride purity of the recovered substance was 98% or more,so that a high purity calcium fluoride crystal was obtained.

However, when fine granules were contained, fine granules with adiameter of lower than 20 μm leaked from the calcium carbonate packedtowers due to carbonic acid gas generated by the reaction of the calciumcarbonate and the hydrogen fluoride. Therefore, when the amount of finegranules with a diameter of lower than 20 μm is small (Example 5), noproblems arise. However, when such fine granules were contained at aratio of 15% or more (Examples 6 and 7), the fluorine removal ratio waslower than 90% in some cases, the treatment became unstable.

TABLE 2 Content of granules with a volume mean CaF₂ diameter of lowerRaw water Treated water purity of than 20 μm of calcium T-F T-F F⁻ Fremoval recovered carbonate granules concentration concentrationconcentration ratio substance % mg/L mg/L mg/L % % Example 4 <1 1000010~30  10~30 >99 >98 Example 5 5 10000 30~300 10~30 97~99 >98 Example 616 10000 200~1100 10~30 89~98 >98 Example 7 25 10000 600~1500 10~3085~94 >98

The invention is described in detail with reference to specific aspects.However, it is clear for a person skilled in the art to alter theaspects in various manners without deviating from the scope of theintention.

This application was made based on Japanese Patent Application (JapanesePatent Application No. 2009-243519) filed on Oct. 22, 2009, the entirecontents of which are incorporated herein by reference.

1. A method for treating fluorine-containing water, comprising: passingfluorine-containing water through calcium carbonate packed towersarranged in series in a plurality of stages to remove fluorine in thefluorine-containing water and recover calcium fluoride, wherein thecalcium carbonate granules packed in each towers have a volume meandiameter of 30 to 150 μm.
 2. The method for treating fluorine-containingwater according to claim 1, wherein the calcium carbonate packed towersare arranged in series in two stages.
 3. The method for treatingfluorine-containing water according to claim 1, wherein the calciumcarbonate granules contain granules with a particle diameter of lowerthan 20 μm at a ratio of 15% or lower.
 4. The method for treatingfluorine-containing water according to claim 1, wherein a volume meandiameter of the calcium carbonate is 30 to 100 μm.
 5. The method fortreating fluorine-containing water according to claim 1, wherein thefluorine-containing water is passed through the calcium carbonate packedtowers at an SV of 0.1 to 5 hr⁻¹.
 6. A device for treatingfluorine-containing water, comprising: a unit for treating thefluorine-containing water in which calcium carbonate packed towers arearranged in series in a plurality of stages; a unit for passing thefluorine-containing water through the unit for treating thefluorine-containing water; a unit for extracting treated water from theunit for treating the fluorine-containing water; and a unit forrecovering calcium fluoride from the calcium carbonate packed towers,wherein a volume mean diameter of the calcium carbonate packed in thecalcium carbonate packed towers is 30 to 150 μm. 7 The device fortreating fluorine-containing water according to claim 6, wherein thecalcium carbonate packed towers are arranged in series in two stages. 8The device for treating fluorine-containing water according to claim 6,wherein the calcium carbonate granules contain granules with a diameterof lower than 20 μm at a ratio of 15% or lower. 9 The device fortreating fluorine-containing water according to claim 6, wherein avolume mean diameter of the calcium carbonate is 30 to 100 μm.
 10. Thedevice for treating fluorine-containing water according to claim 6,wherein an SV of the passage of the fluorine-containing water into thecalcium carbonate packed towers is 0.1 to 5 hr⁻¹.